CN109912881B - Polyolefin resin composition for covering cable comprising heterogeneous rubber component - Google Patents
Polyolefin resin composition for covering cable comprising heterogeneous rubber component Download PDFInfo
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Abstract
The present invention relates to a polyolefin resin composition having excellent low-temperature impact strength, flexibility and thermal stability, and more particularly, to a polyolefin resin composition which is excellent in low-temperature impact strength and flexibility by uniformly dispersing a large amount of a different rubber phase in a polyolefin continuous phase, and which is excellent in heat resistance due to a stable structure of the different rubber phase and the polyolefin continuous phase, and thus can be used as an insulating layer material for cables without being crosslinked.
Description
Technical Field
The present invention relates to a polyolefin resin composition having excellent low-temperature impact strength, flexibility (softness) and thermal stability, and more particularly, to a polyolefin resin composition which is excellent in low-temperature impact strength and flexibility by uniformly dispersing a large amount of a heterogeneous rubber in a polyolefin continuous phase, and which is excellent in heat resistance due to a stable structure of the heterogeneous rubber phase and the polyolefin continuous phase, and thus can be used as an insulating layer material for cables without being crosslinked.
Background
Polypropylene, which is one of polyolefins, has excellent mechanical physical properties and barrier properties, and high thermal stability, but is not suitable for use as a cable insulation material requiring flexibility because of poor impact characteristics at low temperatures and high rigidity. Thus, polyethylene (high density polyethylene, linear low density polyethylene, etc.) is mainly used as an insulating material for power transmission pipes for power transmission and distribution, which requires both cold resistance and flexibility, but the melting point of polyethylene is low and melting or decomposition occurs at high temperatures, so the normal operating temperature is limited to 90 ℃. Since the power transmission efficiency of a distribution cable is improved if the normal operating temperature is increased, polyethylene, ethylene-propylene rubber copolymer, ethylene-propylene-diene rubber copolymer, or the like is crosslinked and used to improve the heat resistance of an insulating material.
However, the crosslinked polymer as described above is difficult to recycle after the end of its service life, and therefore needs to be incinerated or disposed of, and additional equipment required for recycling causes additional costs. Further, there are disadvantages in that there is a high possibility of environmental pollution due to a crosslinking by-product generated during crosslinking, wet crosslinking causes a process of further drying the product, and processability is limited when excessive crosslinking is performed due to heat generated during extrusion.
Therefore, studies have been made to improve flexibility and cold resistance while ensuring heat resistance of polypropylene. For example, U.S. Pat. No. 9,416,207 discloses a polypropylene composition having improved flexibility and transparency by continuously reacting three propylene rubber copolymers. However, the composition is not suitable for use as a cable since it has a very small improvement in impact strength at low temperature and thus is damaged when it is built outdoors or installed and moved according to weather, and has a low melting point and thus a low heat resistance, and thus is not suitable for use as an insulating material for a cable.
Korean laid-open patent application No. 2014-0040082 discloses a thermoplastic polymer material in which a copolymer of an α -olefin comonomer rubber phase and propylene is mixed to secure flexibility. However, if the content of the rubber phase is small, flexibility is reduced when the rubber phase is used as a cable insulating material, and it is difficult to construct and install the cable insulating material.
Further, Korean laid-open patent application No. 1998-0009364 discloses a thermoplastic polyolefin resin composition for interior and exterior materials for automobiles, comprising a polypropylene resin, an ethylene-propylene rubber and an ethylene-alpha-olefin copolymer, but the composition has a relatively high melt index in the range of 12.7 to 20.1g/10 min and a low heat distortion temperature of 61 to 75 ℃, and thus is not suitable for use as an insulating material for cables.
Documents of the prior art
Patent document
(patent document 1) U.S. Pat. No. 9,416,207 (2016.8.16)
(patent document 2) Korean laid-open patent application No. 2014-0040082 (2014.4.2)
(patent document 3) Korean laid-open patent application No. 1998-
Disclosure of Invention
Technical problem to be solved
Accordingly, an object of the present invention is to provide a polyolefin resin composition which is excellent in impact strength and flexibility at low temperatures, while having heat resistance and mechanical physical properties inherent in polyolefins even if a large amount of a rubber phase is contained, and has insulation properties similar to those of conventional materials, and thus is suitable for an insulation layer of a cable.
Technical scheme
In one embodiment of the present invention for achieving the above object, there is provided a polyolefin resin composition comprising: (A)29.8 to 80% by weight, preferably 30 to 80% by weight, of at least one polyolefin resin selected from the group consisting of a propylene homopolymer, an α -olefin-propylene random copolymer and an ethylene-propylene block copolymer; (B)10 to 40% by weight of an ethylene-propylene rubber copolymer resin; and (C)10 to 40% by weight of C4～C8An alpha-olefin-ethylene rubber copolymer resin; the polyolefin resin composition has a melt index of 0.5 to 10g/10 min, a flexural modulus of 100 to 800MPa, a melting temperature of 140 to 170 ℃ and a sum of the resin (B) and the resin (C) of 20 to 70 wt% when measured at 230 ℃ under a load of 2.16 kg.
Preferably, the α -olefin monomer constituting the α -olefin-propylene random copolymer is one or more selected from the group consisting of ethylene, 1-butene, 1-hexene and 1-octene.
More preferably, the α -olefin monomer constituting the α -olefin-propylene random copolymer is ethylene.
More preferably, the content of the α -olefin monomer in the α -olefin-propylene random copolymer is selected so that the melting temperature of the α -olefin-propylene random copolymer is 140 to 170 ℃.
More preferably, the content of the α -olefin monomer in the α -olefin-propylene random copolymer is 2 to 20% by weight in the case of ethylene and 2 to 10% by weight in the case of 1-butene.
Preferably, the ethylene content of the ethylene-propylene block copolymer is 2 to 25% by weight, and the propylene content is 75 to 98% by weight.
Preferably, the polyolefin resin (A) has a melt index of 1 to 10g/10 min, a flexural modulus of 500 to 2,000MPa, and a melt enthalpy of 40 to 100J/g, when measured at 230 ℃ under a load of 2.16 kg.
Preferably, the ethylene-propylene rubber copolymer resin (B) has an ethylene content of 5 to 30% by weight and a propylene content of 70 to 95% by weight.
Preferably, the ethylene-propylene rubber copolymer resin (B) has a melt index of 0.5 to 15g/10 min, a flexural modulus of 100MPa or less, and a melt enthalpy of 20J/g or less, when measured at 230 ℃ under a load of 2.16 kg.
Preferably, composition C4～C8C of the alpha-olefin-ethylene rubber copolymer resin (C)4～C8The alpha-olefin is at least one selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene.
More preferably, composition C4～C8C of alpha-olefin-ethylene rubber copolymer resin4～C8The alpha-olefin is 1-butene, 1-hexene or 1-octene.
More preferably, C4～C8The content of the alpha-olefin monomer in the alpha-olefin-ethylene rubber copolymer resin (C) is 20 to 45 wt% when 1-butene is contained, 10 to 30 wt% when 1-hexene is contained, and 5 to 20 wt% when 1-octene is contained.
Preferably, C is measured at 230 ℃ under a load of 2.16kg4～C8The alpha-olefin-ethylene rubber copolymer resin (C) has a melt index of 0.5 to 20g/10 min,a flexural modulus of 100MPa or less and a melting enthalpy of 10J/g or less.
Preferably, the polyolefin resin composition of the present invention contains 30 to 75% by weight of a propylene monomer, 20 to 50% by weight of an ethylene monomer, and 5 to 20% by weight of an alpha-olefin monomer.
Preferably, the polyolefin resin composition of the present invention may include one or more additives selected from the group consisting of an antioxidant, a neutralizer, a transparent nucleating agent and a long-term heat stabilizer.
More preferably, the content of the additive is in the range of 0.2 to 1% by weight based on the total weight of the polyolefin resin composition.
Preferably, the polyolefin resin composition of the present invention has an Ehrleft's (IZOD) impact strength of 2.0kgfcm/cm or more as measured at-40 ℃.
Preferably, the polyolefin resin composition of the present invention has a volume resistance of more than 1015Ωcm。
Preferably, the intrinsic viscosity of the solvent extract as the rubber component in the polyolefin resin composition of the present invention is 1.0 to 4.0 dl/g.
Effects of the invention
The polyolefin resin composition of the present invention is excellent in low-temperature impact strength and flexibility by uniformly dispersing a large amount of the different rubber phase on the polyolefin continuous phase, is excellent in mechanical physical properties without phase transfer of the continuous phase and the rubber phase, and is excellent in heat resistance and also excellent in insulation strength due to the stable structure of the different rubber phase and the polyolefin continuous phase, and thus can be used as an insulation layer material for cables even without crosslinking, and can be recycled to be environmentally friendly.
Drawings
FIG. 1 is a graph comparing low temperature Ehrleft (IZOD) impact strengths of test pieces prepared from the polyolefin resin compositions of examples 2 and 3 and comparative examples 3 and 4.
FIG. 2 is a photograph of a cross section of a test piece prepared from the polyolefin resin composition of example 3 observed by a scanning electron microscope.
Detailed Description
The present invention will be described in more detail below.
The polyolefin resin composition of one embodiment of the present invention comprises: (A)29.8 to 80% by weight, preferably 30 to 80% by weight, of at least one polyolefin resin selected from the group consisting of a propylene homopolymer, an α -olefin-propylene random copolymer and an ethylene-propylene block copolymer; (B)10 to 40% by weight of an ethylene-propylene rubber copolymer resin; and (C)10 to 40% by weight of C4～C8An alpha-olefin-ethylene rubber copolymer resin; the polyolefin resin composition has a melt index of 0.5 to 10g/10 min, a flexural modulus of 100 to 800MPa, a melting temperature of 140 to 170 ℃ and a sum of the resin (B) and the resin (C) of 20 to 70 wt% when measured at 230 ℃ under a load of 2.16 kg.
In the polyolefin resin composition of the present invention, the polyolefin resin (a) constituting the continuous phase is at least one resin selected from the group consisting of a propylene homopolymer, an α -olefin-propylene random copolymer, and an ethylene-propylene block copolymer.
Among them, the α -olefin monomer constituting the α -olefin-propylene random copolymer includes ethylene, 1-butene, 1-hexene, 1-octene and the like, and ethylene is preferable.
The content of the α -olefin monomer in the α -olefin-propylene random copolymer may be selected so that the melting temperature of the α -olefin-propylene random copolymer is 140 to 170 ℃, and for example, the content may be 2 to 20% by weight in the case of ethylene and 2 to 10% by weight in the case of 1-butene.
The ethylene content of the ethylene-propylene block copolymer may be 2 to 25% by weight, and the propylene content may be 75 to 98% by weight.
The polyolefin resin (A) may have a melt index of 1 to 10g/10 min, a flexural modulus of 500 to 2,000MPa, and a melt enthalpy of 40 to 100J/g, when measured at 230 ℃ under a load of 2.16 kg.
Commercially available polyolefin resins (A) include, but are not limited to, HF11PT (propylene homopolymer consisting of 100% by weight of propylene; Hanwadak (Hanwatotal)), RF401 (ethylene-propylene random copolymer consisting of 98% by weight of propylene and 2% by weight of ethylene; Hanwata (Hanwata)) and CF330 (ethylene-propylene block copolymer consisting of 94% by weight of propylene and 6% by weight of ethylene; Hanwadak (Hanwata)), CF309 (ethylene-propylene block copolymer consisting of 94% by weight of propylene and 6% by weight of ethylene; Hanwadak (Hanwata)), and the like.
In the polyolefin resin composition of the present invention, one of the resins (B) constituting the rubber phase is an ethylene-propylene rubber copolymer. The ethylene content in the ethylene-propylene rubber copolymer may be 5 to 30% by weight, and the propylene content may be 70 to 95% by weight.
The ethylene-propylene rubber copolymer resin (B) may have a melt index of 0.5 to 15g/10 min, a flexural modulus of 100MPa or less, and a melt enthalpy of 20J/g or less, when measured at 230 ℃ under a load of 2.16 kg. Further, the resin (B) is dissolved in xylene (xylene) at a concentration of 1% for 1 hour at 140 ℃, and then the weight of the solvent extract extracted after 2 hours at normal temperature is 75 to 100% of the original weight, and the intrinsic viscosity of the solvent extract measured in decalin (decalin) solution at 135 ℃ using a viscosity measuring instrument may be 1.0 to 3.0 dl/g.
Examples of the commercially available ethylene-propylene rubber copolymer resin (B) include, but are not limited to, Versify (Dow), Vistamaxx (ExxonMobil), Tafmer (Mitsui), KEP (Kumho Petrochemical), and the like.
In the polyolefin resin composition of the invention, the additional resin (C) constituting the rubber phase is at least one C4～C8Alpha-olefin-ethylene rubber copolymers.
Composition C4～C8C of alpha-olefin-ethylene rubber copolymer resin4～C8Examples of the α -olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, and 1-butene, 1-hexene or 1-octene is preferable. Wherein, C4～C8The content of the alpha-olefin monomer in the alpha-olefin-ethylene rubber copolymer resin can be 20-45 wt% when the content is 1-butene, and 10-30 wt% when the content is 1-hexeneThe amount of 1-octene may be 5 to 20% by weight.
C when measured at 230 ℃ under a load of 2.16kg4～C8The alpha-olefin-ethylene rubber copolymer resin (C) may have a melt index of 0.5 to 20g/10 min, a flexural modulus of 100MPa or less, and a melt enthalpy of 10J/g or less. Further, the resin (C) is dissolved in xylene (xylene) at a concentration of 1% for 1 hour at 140 ℃, and then the weight of the solvent extract extracted after 2 hours at normal temperature is 75 to 100% of the original weight, the intrinsic viscosity of the solvent extract measured in decalin (decalin) solution at 135 ℃ using a viscosity measuring instrument may be 1.0 to 3.0dl/g, and the glass transition temperature may be-40 ℃ or lower.
Commercially available C4～C8Examples of the α -olefin-ethylene rubber copolymer resin (C) include Engage (Dow), Exact (ExxonMobil), Lucene (LG Chemical), Tafmer (Mitsui), and Solumer (SK Chemical), but are not limited thereto.
The polyolefin resin composition of the present invention contains the polyolefin resin (A) constituting the continuous phase in an amount of 29.8 to 80% by weight, preferably 30 to 80% by weight. If the content of the polyolefin resin (A) is less than 29.8% by weight, it is difficult to constitute the continuous phase, and if the content of the polyolefin resin (A) exceeds 80% by weight, the flexural modulus is large and the flexibility is lowered.
In the polyolefin resin composition of the invention, the ethylene-propylene rubber copolymer resins (B) and C constituting the rubber phase4～C8The content of the alpha-olefin-ethylene rubber copolymer resin (C) is 10 to 40 wt% respectively. When the content of each of the resin (B) and the resin (C) exceeds 40%, the amount of one rubber phase component is excessive, and the heat resistance, tensile strength, flexural modulus, and the like depending on the structure of the polypropylene-based resin of the continuous phase are lowered. When the content of each of the resin (B) and the resin (C) is less than 10%, the content of the polyolefin resin (a) is high and the flexural modulus is large, so that flexibility is reduced, and the effect of improving the low-temperature impact strength by the resin (B) and the resin (C) constituting the rubber phase cannot be expected.
In the polyolefin resin composition of the present invention, the sum of the contents of the resin (B) and the resin (C) constituting the rubber phase is in the range of 20 to 70% by weight. When the content of the two rubber copolymer resins (B) and (C) exceeds 70%, the amount of the entire rubber phase is too large, and the heat resistance, tensile strength, flexural modulus, and the like depending on the structure of the polypropylene-based resin of the continuous phase are lowered. Further, when the contents of the two rubber copolymer resins (B) and (C) are less than 20%, the flexural modulus is large and the flexibility is lowered, and the effect of improving the low-temperature impact strength by the resins (B) and (C) cannot be expected.
When the polyolefin resin composition of the present invention is dissolved in xylene (xylene) solvent and analyzed, it shows a composition ratio of 30 to 75% by weight of a propylene monomer, 20 to 50% by weight of an ethylene monomer, and 5 to 20% by weight of an alpha-olefin monomer other than the propylene monomer. With such a composition ratio, the continuous phase is composed of propylene, so that heat resistance and electrical characteristics are excellent, and the composition has a low glass transition temperature due to the α -olefin monomer, so that low temperature impact properties are increased, and the content of the rubber copolymer in the continuous phase is increased due to the content of ethylene, so that flexibility is improved. If the content of the propylene monomer is less than the above range, the continuous phase may be composed of other phases and thus the heat resistance characteristics may be lost, and if the content of the propylene monomer is more than the above range, the bending modulus may be high and thus the mountability and the impact characteristics may be degraded.
The polyolefin resin composition of the present invention may contain additives such as an antioxidant, a neutralizer, a transparent nucleating agent, and a long-term heat stabilizer, in addition to the above-mentioned resin components, within a range not inconsistent with the characteristics of the present invention. For example, pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) (Irganox 1010) prepared by Ciba Specialty Chemicals may be used as the antioxidant, and hydrotalcite (Hycite 713) prepared by Ciba Specialty Chemicals may be used as the neutralizing agent for removing residual catalyst.
Preferably, the content of the additive may be in the range of 0.2 to 1% by weight based on the total weight of the polyolefin resin composition.
The polyolefin resin composition of the present invention has a melt index ranging from 0.5 to 10g/10 min when measured at 230 ℃ under a load of 2.16 kg. If the melt index of the polyolefin resin composition is less than 0.5g/10 min, the load is increased during extrusion processing, and productivity is reduced, and if the melt index of the polyolefin resin composition exceeds 10g/10 min, the melt tension of the polyolefin resin composition is low, and sagging occurs during processing, and thus the polyolefin resin composition has a non-uniform appearance, and thus electrical characteristics are greatly reduced.
The polyolefin resin composition of the present invention has a flexural modulus in the range of 100 to 800 MPa. When the flexural modulus is lower than this range, the heat resistance and strength characteristic of polypropylene are lowered, and when the flexural modulus is higher than this range, the rigidity is high and the flexibility is not easy, so that it is difficult to transport cables and wire.
The polyolefin resin composition of the present invention has a melting temperature in the range of 140 to 170 ℃. When the melting temperature of the polyolefin resin composition is less than 140 ℃, a phenomenon in which a part of the insulating layer is melted due to temperature rise at the time of transient overvoltage occurs, and thus the cable is damaged may occur. When the melting temperature of the polyolefin resin composition is higher than 170 ℃, the flexural modulus is too large to improve the resin composition to have flexibility.
Further, the polyolefin resin composition of the present invention may have an Ehrleft (IZOD) impact strength of 2.0kgfcm/cm or more as measured at-40 ℃ according to the American Society for Testing and Materials (ASTM). The low temperature impact strength of a typical propylene homopolymer or ethylene-propylene block copolymer depends on the ratio of ethylene and propylene monomers of the continuous and rubber phases. When the content of ethylene is high, the low-temperature impact strength increases, but when the content of ethylene is increased while propylene is polymerized into the continuous phase, ethylene is polymerized in the continuous phase, and the heat resistance of the continuous phase decreases. Therefore, the commercially used polypropylene composition exhibits a glass transition temperature of 0 to 10 ℃ and-30 to-20 ℃ so that the content of the rubber at-40 ℃ is not related to the impact strength, and the impact strength is not improved even if the content of the rubber phase is increased.
Thus, the polypropylene composition of the prior art has an Ehrleft's (IZOD) impact strength at-40 ℃ measured according to ASTM of less than 2.0 kgfcm/cm.
On the other hand, in the polyolefin resin composition of the present invention, a large amount of the foreign rubber phase is uniformly dispersed on the polypropylene continuous phase, and the ethylene content in the ethylene- α -olefin rubber is high, so that the glass transition temperature is observed at-40 ℃ or lower, and therefore the Ehrleft impact strength at-40 ℃ may be 2.0kgfcm/cm or higher.
The polyolefin resin composition of the present invention has a volume resistance of 1015Omega cm or more, preferably 1016Omega cm or more, and is suitable for use as an insulator of a high-voltage cable. If the content of the rubber phase in the polyolefin resin composition is excessive, the volume resistance of the composition is less than 1015Ω cm, and thus is not suitable for use as an insulating material.
In the polyolefin resin composition of the present invention, the intrinsic viscosity of the solvent extract as the rubber component is preferably 1.0 to 4.0 dl/g. When the intrinsic viscosity is less than 1, the impact strength of the rubber cannot be improved, and when the intrinsic viscosity exceeds 4.0, the processability is lowered and whitening occurs.
[ examples ]
The present invention will be described in more detail below with reference to examples and comparative examples. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited thereto.
The resin components and additives used in the following examples and comparative examples are as follows.
A1: propylene homopolymer consisting of 100% by weight of propylene (Hanwha Total; HF11PT)
A2: ethylene-propylene random copolymer composed of 98% by weight of propylene and 2% by weight of ethylene (Hanwhatal, Handada); RF401)
A3: ethylene-propylene block copolymer composed of 94% by weight of propylene and 6% by weight of ethylene (Hanwhatal, Korean Douda Corp.; CF330)
B1: ethylene-propylene rubber copolymer consisting of 75% by weight of propylene and 25% by weight of ethylene (melt index 2; melting temperature (Tm) 160 ℃ C.)
B2: ethylene-propylene rubber copolymer composed of 80% by weight of propylene and 20% by weight of ethylene (ExxonMobil; Vistamaxx 6202)
B3: ethylene-propylene rubber copolymer consisting of 85% by weight of propylene and 15% by weight of ethylene (Dow; Versify 2400)
C1: a1-hexene-ethylene rubber copolymer comprising 15 wt% of 1-hexene and 85 wt% of ethylene is prepolymerized by a metallocene catalyst, and polymerized at a temperature of 70 to 80 ℃ and a pressure of 10 to 30 atm in the absence of a hydrocarbon solvent, and has a melt index of 3 and a Tm of 115 ℃.
C2: 1-octene-ethylene rubber copolymer consisting of 15 wt% 1-octene and 85 wt% ethylene (Dow); Engage 8842)
Antioxidant: pentaerythrityl tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) (Ciba Specialty Chemicals; Irganox 1010)
Neutralizing agent: hydrotalcite (Ciba Specialty Chemicals, Hycite 713)
Example 1
Prepared by the process described below from (a)74.8 wt% of a polyolefin resin a 1; (B) 10% by weight of a rubber copolymer resin B1; (C) 15% by weight of a rubber copolymer resin C1; and 0.2 wt% of an antioxidant and a neutralizing agent.
The above three polyolefin resins (A), (B) and (C) and the antioxidant and neutralizer were mixed in a Henschel mixer (SSM-75) for 30 minutes, then melt-extruded at 230 ℃ through a twin-screw extruder PLATEK (TEK-30) and pelletized by a pelletizer. The resin composition pellets thus prepared were injection-molded into test pieces specified in ASTM4 by using a 150-ton injection molding machine (selexte 150).
Examples 2 to 4 and comparative examples 1 to 6
Compositions were prepared by the same method as example 1, except that the kind and content of the resin constituting the composition were changed as shown in table 1 below. The numerals shown in table 1 below indicate the contents in wt%.
[ Table 1]
The physical properties of the compositions prepared in examples 1 to 4 and comparative examples 1 to 6 were measured according to the methods and standards described below. The results are shown in table 2 below.
(1) Melt index (melt index)
Measurements were made at 230 ℃ with a load of 2.16kg using a CEAST MF10 apparatus, according to ASTM D1238 conditions.
(2) Content of solvent extract (xylene soluble)
The polypropylene resin was dissolved in xylene (xylene) at a concentration of 1% for 1 hour at 140 c, and then extracted after two hours at normal temperature, to measure the weight thereof, and expressed as a percentage with respect to the entire weight of the polypropylene resin.
(3) Intrinsic viscosity of solvent extract
The intrinsic viscosity of the solvent extract was measured in decalin (decalin) solution at 135 ℃ using a viscosity measuring instrument.
(4) Melting temperature
The sample was kept at a constant temperature of 200 ℃ for 10 minutes by using a Q2000 Differential Scanning Calorimeter (DSC) of TA instruments (TA Instrument) to remove the thermal history, and then cooled from 200 ℃ to 30 ℃ at 10 ℃ per minute to crystallize with the same thermal history, then kept at a constant temperature of 30 ℃ for 10 minutes, and again heated at 10 ℃ per minute, and the melting temperature (Tm) was determined from the peak temperature.
(5) Flexural modulus of elasticity (FM)
Test pieces prepared according to ASTM D790 were injection molded and then left at 23. + -. 2 ℃ and 50. + -. 5% Relative Humidity (RH) for 48 hours, after which they were measured within 72 hours using a UTM instrument. The distance between the support points on both sides of the test piece was 48mm and the measurement was carried out at a rate of 5 mm/min.
(6) Cold impact resistance
Test pieces having a length of 38mm, a width of 6mm and a thickness of 2mm were injection-molded at an injection temperature of 240 ℃ and 5 test pieces were subjected to a cold impact resistance test at-40 ℃ according to KS C3004 to obtain the number of damaged test pieces. The test piece was judged to pass when the number of the damaged test pieces was 1 or less, and the test piece was judged to fail when the number of the damaged test pieces exceeded 1.
(7) Ehrleft's (IZOD) impact strength (-40 ℃ C.)
The prepared injection-molded test pieces were molded into 5 pieces or more, and then left at 23. + -. 2 ℃ and 50. + -. 5% Relative Humidity (RH) for 48 hours, after which measurement was carried out within 72 hours. The samples having the notch defined in ASTM D256 were stored in a refrigerated storage chamber maintained at-40 ℃ for at least 2 hours or more, and then the test was carried out within 30 minutes. The pendulum was fixed at the designated position, then subjected to a rotational movement with a pendulum weight of 30kg, and the value at the time of damage was recorded, repeated 5 times and the average value was calculated. The Ehrleft's impact strengths of examples 2 and 3 and comparative examples 3 and 4 are shown in FIG. 1.
(8) Deformation by heating
A test piece having a length of 30mm, a width of 15mm and a thickness of 2mm was injection-molded at an injection temperature of 240 ℃ and a load of 1.6kg was applied at 130 ℃ for 6 hours according to KS C IEC 60811-508 method to obtain a deformed thickness, and the deformed thickness was divided by the initial thickness to obtain a deformation ratio. When the heat distortion is less than 50%, the evaluation is passed, and when the heat distortion is 50% or more, the evaluation is failed.
(9) Breakdown voltage of AC insulation
The polypropylene test pieces were prepared into sheets (sheets) of 200 μm thickness by using a laboratory extruder (HAAKE extruder). The AC insulation breakdown voltage was measured at ordinary temperature according to ASTM D149-92 method using spherical electrodes (sphere electrodes) having a diameter of 12.7 mm.
(10) Volume resistance
A flat sheet (sheet) was prepared according to ASTM D257 method and measured using HIRESTAUX8000 from Mitsubishi Chemical company (Mitsubishi Chemical).
(11) Dispersed state of rubber phase
The rubber phase of the section of the test piece prepared from the polyolefin resin composition of example 3 was dissolved using a xylene solvent, and then a photograph observed by a scanning electron microscope was shown in fig. 2.
(12) Tensile strength and elongation
A test piece injection-molded according to ASTM No. 4 was left at 23. + -. 2 ℃ and 50. + -. 5% Relative Humidity (RH) for 48 hours, after which the load was measured while being stretched at a speed of 50 mm/min within 72 hours with a UTM apparatus. The tensile strength at break and elongation were calculated by measuring the load and length of the stretched test piece at the moment of break.
[ Table 2]
NA: low value to be immeasurable
As is apparent from table 2 and fig. 1, the polyolefin resin compositions prepared according to the examples falling within the scope of the present invention are excellent in low-temperature impact strength and flexibility, excellent in mechanical physical properties because no phase transfer of the continuous phase and the rubber phase occurs, and excellent in insulation strength while excellent in heat resistance characteristics because of the stable structure of the heterogeneous rubber phase and the polyolefin continuous phase. Further, as can be seen from fig. 2, the heterogeneous rubber phase of the polyolefin resin composition prepared according to the example of the present invention was uniformly dispersed on the polyolefin continuous phase.
On the other hand, at least one of the above physical properties of the polyolefin resin compositions prepared according to the comparative examples, which do not fall within the scope of the present invention, showed poor results.
Claims (14)
1. Insulation layer for electric cableCharacterized in that the composition comprises: (A)29.8 to 80% by weight of at least one polyolefin resin selected from the group consisting of a propylene homopolymer, an α -olefin-propylene random copolymer and an ethylene-propylene block copolymer; (B)10 to 40% by weight of an ethylene-propylene rubber copolymer resin; and (C)10 to 40% by weight of C4～C8An alpha-olefin-ethylene rubber copolymer resin; the polyolefin resin composition has a melt index of 0.5 to 10g/10 min, a flexural modulus of 100 to 800MPa, a melting temperature of 140 to 170 ℃ and a volume resistance of more than 10 when measured at 230 ℃ under a load of 2.16kg15Ω · cm, wherein the sum of the contents of the resin (B) and the resin (C) is 20 to 70% by weight, and the polyolefin resin (A) has a melt index of 1 to 10g/10 min, a flexural modulus of 500 to 2,000MPa, and a melt enthalpy of 40 to 100J/g, when measured at 230 ℃ under a load of 2.16 kg; the ethylene-propylene rubber copolymer resin (B) has a melt index of 0.5 to 15g/10 min, a flexural modulus of 100MPa or less, a melting enthalpy of 20J/g or less, and contains 5 to 30 wt% of ethylene and 70 to 95 wt% of propylene, when measured at 230 ℃ under a load of 2.16 kg.
2. The polyolefin resin composition according to claim 1, wherein the α -olefin monomer constituting the α -olefin-propylene random copolymer is one or more selected from the group consisting of ethylene, 1-butene, 1-hexene and 1-octene.
3. The polyolefin resin composition according to claim 2, wherein the α -olefin monomer constituting said α -olefin-propylene random copolymer is ethylene.
4. The polyolefin resin composition according to claim 2, wherein the content of the α -olefin monomer in the α -olefin-propylene random copolymer is selected so that the melting temperature of the α -olefin-propylene random copolymer is 140 to 170 ℃.
5. The polyolefin resin composition according to claim 4, wherein the content of the α -olefin monomer in the α -olefin-propylene random copolymer is 2 to 20% by weight in the case of ethylene and 2 to 10% by weight in the case of 1-butene.
6. The polyolefin resin composition according to claim 1, wherein the ethylene content of the ethylene-propylene block copolymer is 2 to 25% by weight, and the propylene content is 75 to 98% by weight.
7. The polyolefin resin composition according to claim 1, wherein said C is composed of4～C8C of the alpha-olefin-ethylene rubber copolymer resin (C)4～C8The alpha-olefin is at least one selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene.
8. The polyolefin resin composition according to claim 7, wherein said C is composed of4～C8C of the alpha-olefin-ethylene rubber copolymer resin (C)4～C8The alpha-olefin is 1-butene, 1-hexene or 1-octene.
9. The polyolefin resin composition according to claim 7, wherein said C is4～C8The content of the alpha-olefin monomer in the alpha-olefin-ethylene rubber copolymer resin (C) is 20 to 45 wt% when 1-butene is contained, 10 to 30 wt% when 1-hexene is contained, and 5 to 20 wt% when 1-octene is contained.
10. The polyolefin resin composition according to claim 1, wherein said C is C when measured at 230 ℃ under a load of 2.16kg4～C8The alpha-olefin-ethylene rubber copolymer resin (C) has a melt index of 0.5 to 20g/10 min, a flexural modulus of 100MPa or less, and a melt enthalpy of 10J/g or less.
11. The polyolefin resin composition according to claim 1, wherein the composition contains 30 to 75% by weight of a propylene monomer, 20 to 50% by weight of an ethylene monomer, and 5 to 20% by weight of an α -olefin monomer.
12. The polyolefin resin composition according to claim 1, wherein said composition has an Ehrzel's impact strength of 2.0kgfcm/cm or more as measured at-40 ℃.
13. The polyolefin resin composition according to claim 1, wherein the intrinsic viscosity of the solvent extract as a rubber component in the composition is 1.0 to 4.0 dl/g.
14. The polyolefin resin composition according to claim 1, wherein the composition comprises 30 to 80% by weight of the polyolefin resin (A).
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| KR10-2017-0170052 | 2017-12-12 | ||
| KR1020170170052A KR101943224B1 (en) | 2017-12-12 | 2017-12-12 | Polyolefin Resin Composition Comprising Different Rubber Components for Insulating Electric Cables |
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| JP7342634B2 (en) * | 2019-11-08 | 2023-09-12 | 住友電気工業株式会社 | Resin composition molded body and power cable |
| EP4056645A4 (en) | 2019-11-08 | 2022-12-07 | Sumitomo Electric Industries, Ltd. | Resin composition, molded body of resin composition, and power cable |
| WO2021210945A1 (en) * | 2020-04-17 | 2021-10-21 | 엘에스전선 주식회사 | Insulation composition, and power cable having insulation layer formed therefrom |
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